CN103814417A - Method for manufacturing ferromagnetic iron nitride powder, anisotropic magnet, bond magnet, and compressed-powder magnet - Google Patents

Method for manufacturing ferromagnetic iron nitride powder, anisotropic magnet, bond magnet, and compressed-powder magnet Download PDF

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Publication number
CN103814417A
CN103814417A CN201280045918.7A CN201280045918A CN103814417A CN 103814417 A CN103814417 A CN 103814417A CN 201280045918 A CN201280045918 A CN 201280045918A CN 103814417 A CN103814417 A CN 103814417A
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China
Prior art keywords
ferromagnetism
iron
particle powder
manufacture method
nitrided
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CN201280045918.7A
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Inventor
山本真平
高野干夫
高桥研
小川智之
小林齐也
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Tohoku University NUC
Toda Kogyo Corp
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Tohoku University NUC
Toda Kogyo Corp
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Priority claimed from JP2011208189A external-priority patent/JP5924657B2/en
Application filed by Tohoku University NUC, Toda Kogyo Corp filed Critical Tohoku University NUC
Publication of CN103814417A publication Critical patent/CN103814417A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/06—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder
    • H01F1/065—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder obtained by a reduction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/06—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder
    • H01F1/08—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
    • H01F1/083—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together in a bonding agent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/20—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder
    • H01F1/22—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
    • H01F1/24—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together the particles being insulated

Abstract

The present invention provides a ferromagnetic iron nitride powder of especially fine particles, and a manufacturing method therefor. The present invention relates to a method for manufacturing a ferromagnetic iron nitride powder characterised in that an iron compound is mixed with at least one compound selected from among a metal hydride, a metal halide and a metal borohydride, metallic iron obtained by heat treatment of the resulting mixture is mixed with a nitrogen-containing compound, and the resulting mixture is heat treated. In the manufacturing method of the present invention, the nitridation step and reduction step for the iron compound are performed in the same step, at least one compound selected from among a metal hydride, a metal halide and a metal borohydride is used as the reducing agent in the reduction step, and the nitrogen-containing compound is used as the nitrogen source in the nitridation step.

Description

Manufacture method, anisotropic magnet, binding magnet and the powder magnet of ferromagnetism nitrided iron particle powder
Technical field
The present invention relates to ferromagnetism nitrided iron particle powder, particularly relate to the manufacture method of the ferromagnetism nitrided iron particle powder of particulate.In addition, the invention still further relates to the anisotropic magnet, binding magnet and the powder magnet that comprise the ferromagnetism nitrided iron particle powder that utilizes this manufacture method manufacture.
Background technology
Now, the household electrical appliance of hybrid vehicle and electric automobile, air-conditioning and washing machine etc. etc. are seen everywhere, and the magnet of using as the motor of required power-moment of torsion uses Nd-Fe-B based magnetic powder, formed body.But, at present Nd-Fe-B based magnet material there is theoretical boundary as magnet.
And, the rare earth element raw material of the aspect very attractive such as cheap and radioisotope containing ratio is low at cost of material, its import depends on China to a great extent, occurs the significant problem of so-called " Chinese risk ".Therefore, do not contain the Fe of rare earths 16n 2get most of the attention Deng Fe-N based compound.
In Fe-N based compound, known α " Fe 16n 2it is the metastable compound of crystallization when solid solution is had to the martensite of nitrogen or ferrite long term annealing.This α " Fe 16n 2crystallization be bct structure, expect as thering is the huge magnetisable material of large saturation magnetization.But, as common metastable compound, chemically that this compound is few with the synthetic report of the powder that separates separately.
Up to now, in order to obtain α " Fe 16n 2single-phase, attempt the whole bag of tricks such as vapour deposition method, MBE method (molecular beam epitaxy), ion implantation, sputtering method, ammonia nitriding method.But, generate more stable γ '-Fe 4n or ε-Fe 2～3n, and there is the eutectic of martensite (α '-Fe) or ferrite (α-Fe) sample metal, separate separately and manufacture α " Fe 16n 2single compound has difficulties.Although obtained α " Fe with part filminess 16n 2single compound, but the application of film in magnetic material exists limit, is not suitable for launching in purposes widely.
As about α " Fe 16n 2prior art, following technology has been proposed.
Formerly technical literature
Patent documentation
Patent documentation 1: Japanese kokai publication hei 11-340023 communique
Patent documentation 2: TOHKEMY 2000-277311 communique
Patent documentation 3: TOHKEMY 2009-84115 communique
Patent documentation 4: TOHKEMY 2008-108943 communique
Patent documentation 5: TOHKEMY 2008-103510 communique
Patent documentation 6: TOHKEMY 2007-335592 communique
Patent documentation 7: TOHKEMY 2007-258427 communique
Patent documentation 8: TOHKEMY 2007-134614 communique
Patent documentation 9: TOHKEMY 2007-36027 communique
Patent documentation 10: TOHKEMY 2009-249682 communique
Non-patent literature
Non-patent literature 1:M.Takahashi, H.Shoji, H.Takahashi, H.Nashi, T.Wakiyama, M.Doi, and M.Matsui, J.Appl.Phys., Vol.76, pp.6642-6647,1994.
Non-patent literature 2:Y.Takahashi, M.Katou, H.Shoji, and M.Takahashi, J.Magn.Magn.Mater., Vol.232, p.18-26,2001.Y.Takahashi, M.Katou, H.Shoji, and M.Takahashi, J.Magn.Magn.Mater., Vol.232, p.18-26,2001.
Summary of the invention
The technical task that invention will solve
In the technology of above-mentioned patent documentation 1～11 and non-patent literature 1,2 records, also still insufficient.
, the iron particle of having recorded in patent documentation 1 having surface oxidation overlay film reduces after processing, carries out nitrogen treatment, obtains Fe 16n 2, but do not consider the problem that improves maximum magnetic energy product.In addition, nitridation reaction needs long-time, is difficult to be suitable for industrial.
In addition, in patent documentation 2, record croci is reduced and processes generation metallic iron powder, the metallic iron powder obtaining has been carried out to nitrogen treatment and obtain Fe 16n 2, but be hardly suitable as magnetic recording media magnetic-particle powder, hope has a high maximum magnetic energy product BH maxretentive material.
In addition, in patent documentation 3～9, record and be changed to the very big magnetisable material that ferritic magnetic recording material is used, but can not get α " Fe 16n 2single-phase, more stable γ '-Fe 4n or ε-Fe 2～ 3n, martensite (α '-Fe) or ferrite (α-Fe) sample metal generate as mixed phase.
In addition, in patent documentation 10, be necessary although add element, do not discuss in detail about its necessity, and about the magnetic characteristic of the product obtaining, be suitable as hardly and wish to have high maximum magnetic energy product BH maxretentive material.
In non-patent literature 1～2, successfully obtain the α " Fe of filminess 16n 2single-phase, but there is limit in film, be not suitable in purposes expansion widely in being suitable for.In addition, make general magnetic material and exist the problem of productivity ratio and economy.
Therefore, object of the present invention is particularly in a kind of ferromagnetism nitrided iron (Fe that can easily obtain particulate is provided 16n 2) manufacture method of ferromagnetism nitrided iron particle powder of particle powder.
For the technological means of technical solution problem
Above-mentioned problem can solve by following the present invention.
That is, the present invention is a kind of manufacture method of ferromagnetism nitrided iron particle powder, it is characterized in that, by metallic iron or iron compound and nitrogen-containing compound mixing, then heat-treats (the present invention 1).
In addition, the present invention is the manufacture method of the ferromagnetism nitrided iron particle powder described in the present invention 1, and metallic iron and nitrogen-containing compound are mixed, and the average grain long axis length of metallic iron is 5～300nm(the present invention 2).
In addition, the present invention is the manufacture method of the ferromagnetism nitrided iron particle powder described in the present invention 2, as metallic iron, the metallic iron (the present invention 3) that uses more than at least a kind that will be selected from metal hydride, metal halide, metallic boron hydrides compound and iron compound to mix, then heat-treat and obtain.
In addition, the present invention is the manufacture method of the ferromagnetism nitrided iron particle powder described in the present invention 2 or 3, as metallic iron, uses the metallic iron (the present invention 4) that carries out coated with silica with the thickness below 20nm.
In addition, the present invention is the manufacture method of the ferromagnetism nitrided iron particle powder described in the present invention 1, and iron compound, nitrogen-containing compound and reducing agent are mixed, and then heat-treats (the present invention 5).
In addition, the present invention is the manufacture method of the ferromagnetism nitrided iron particle powder described in the present invention 5, carries out reduction operation and the nitrogenize operation (the present invention 6) of iron compound in same operation.
In addition, the present invention is the manufacture method of the ferromagnetism nitrided iron particle powder described in the present invention 5 or 6, as the reducing agent in reduction operation, use is selected from least a kind of above compound in metal hydride, metal halide, metallic boron hydrides, and, as the nitrogenous source of nitrogenize operation, use nitrogen-containing compound (the present invention 7).
In addition, the present invention is the manufacture method of the ferromagnetism nitrided iron particle powder described in any one in the present invention 5～7, as iron compound, uses the iron compound (the present invention 8) of coated with silica.
In addition, the present invention is a kind of manufacture method of anisotropic magnet, this anisotropic magnet comprises ferromagnetism nitrided iron particle powder, this manufacture method is characterised in that, uses the ferromagnetism nitrided iron particle powder (the present invention 9) making by the manufacture method of the ferromagnetism nitrided iron particle powder described in any one in the present invention 1～8.
In addition, the manufacture method that the present invention is a kind of binding magnet, this binding magnet contains ferromagnetism nitrided iron particle powder, and this manufacture method is characterised in that, uses the ferromagnetism nitrided iron particle powder (the present invention 10) described in any one in the present invention 1～8.
In addition, the present invention is a kind of manufacture method of powder magnet, this powder magnet contains ferromagnetism nitrided iron particle powder, this manufacture method is characterised in that, uses the ferromagnetism nitrided iron particle powder (the present invention 11) making by the manufacture method of the ferromagnetism nitrided iron particle powder described in any one in the present invention 1～8.
Invention effect
The manufacture method of ferromagnetism nitrided iron particle powder of the present invention can easily obtain the ferromagnetism nitrided iron particle powder of ferromagnetism nitrided iron particle powder, particularly particulate, therefore, is suitable as the manufacture method of ferromagnetism nitrided iron particle powder.Particularly owing to using nitrogen-containing compound in nitrogen treatment, thereby compared with existing Gaseous Nitriding processing, nitrogenize efficiency is very excellent, and, can also reduce operation and nitrogenize operation by iron compound simultaneously, as industrial manufacture method, there is very high value.
Embodiment
The manufacture method of ferromagnetism nitrided iron particle powder of the present invention is characterised in that, by metallic iron or iron compound and nitrogen-containing compound mixing, then heat-treats.Its feature is particularly in using nitrogen-containing compound this point, with the reacting of nitrogen-containing compound, can be divided into the method (the present invention 2) of the metallic iron with specific average grain long axis length and the method (the present invention 5) that iron compound is reacted with reducing agent of using.Below, the method to the present invention 2 and the present invention's 5 method describes respectively, in the absence of special instruction, is the method to the present invention 2 and the present invention's 5 the common explanation of method.
First, the present invention 2 method is described.
First, the metallic iron using in the present invention 2 method is described.
The average grain long axis length of the metallic iron raw material in the present invention 2 method is 5～300nm.In the metallic iron lower than 5nm, the iron atom contacting with particle surface interface exists in a large number, therefore, even if obtain ferromagnetism nitrided iron particle powder, can not expect large magnetization.When average grain long axis length exceedes 300nm, nitrogenize is difficult to carry out, metallic iron and Fe 4n etc. mix existence.Preferred average grain long axis length is 5～275nm, more preferably 6～265nm.
The metallic iron raw material that is used for the ferromagnetism nitrided iron particle powder of the method that obtains the present invention 2, can use polyalcohol method, IBM method, micella/reversed micelle method, the precipitation method etc. to make, and is not particularly limited.Can also iron compound reduction be obtained with hydrogen etc.
For example, the metallic iron raw material in the present invention 2 method can by will be selected from least a kind of above compound (reducing agent) in metal hydride, metal halide, metallic boron hydrides and iron compound mix and heat-treat and obtain.As the concrete example of these reducing agents, can enumerate: the metal hydrides such as dimethyl hydrogenation aluminium, diisobutyl aluminium hydride, calcium hydride, magnesium hydride, sodium hydride, hydrofining, lithium hydride, titantium hydride, zircoium hydride, the metal halide such as magnesium borohydride, sodium borohydride, or the metallic boron hydrides such as isopropyl halogenation magnesium, gallium halide, indium halide, tin halides, zinc halide, halogenation cadmium, copper halide, nickel halogenide, manganese halide, sodium aluminum hydride.These reducing agents can use one, also can use two or more simultaneously.Ratio while using two or more reducing agents is not particularly limited.
As above-mentioned iron compound, alpha-feooh, β-FeOOH, γ-FeOOH, α-Fe 2o 3, β-Fe 2o 3, Fe 3o 4, γ-Fe 2o 3, ferric oxalate, ferric acetate, ferric nitrate, ferric stearate, iron oleate etc. all can, be not particularly limited.In addition, can use one, also can use two or more simultaneously.Use the ratio of the each compound when two or more to be not particularly limited.Shape is not particularly limited, can be needle-like, spindle shape, grain of rice shape, spherical, granular, hexahedron shape, octahedra shape etc. any.
In the situation that using FeOOH, while carrying out processed as required, the temperature of processed is preferably 80～350 ℃.When they are during lower than 80 ℃, dewater hardly.In the time that it exceedes 350 ℃, in ensuing reduction is processed, be difficult to obtain at low temperatures iron granule powder.More preferably processed temperature is 85～300 ℃.
It is in good condition that reducing agent carries out as powder and iron granule powder that dry type mixes, and preferably with mortar etc., iron granule powder and reducing agent pulverized, mixed in advance.
In addition, particularly in reducing agent, contain the situation of water constituent and the absorption of moisture violent, be preferably dried in advance or the pre-heat treatment.
The blending ratio of iron granule powder and reducing agent is not particularly limited, and is 0.5～20 with respect to the weight ratio of iron granule powder, is preferably 0.8～10.
The purity of reducing agent is not particularly limited.While considering the validity of reducing agent and cost, for example, be 50～99%, be preferably 60～96%.
As the method that the mixture of iron granule powder and reducing agent is heat-treated, standing type, mobile any all can, preferably in closed container, carry out.If under laboratory level, for example, can consider the method for the mixture of enclosing iron granule powder and reducing agent in glass tube.In addition, pilot plant's scale if can be for enclosing the mixture of iron granule powder and reducing agent on one side and it flowed, the method for heat-treating on one side in metal tube.
The heat treatment temperature of the mixture of iron granule powder and reducing agent is 50～280 ℃.The reduction temperature that heat treatment temperature has separately according to the kind of reducing agent and addition, metallic compound is determined, is preferably 80～275 ℃, more preferably 100 ℃～250 ℃.In addition, the heat treated time is preferably 0.5 hour～and 7 days, more preferably 1 hour～3 days.
Metallic iron in the present invention 2 method can be by coated with silica.Coated with silica thickness is below 20nm.Be preferably below 17nm.
The nitrogen-containing compound that the present invention 2 method is used, for solid or liquid such as urea, ammoniacal liquor, ammonium chloride, nitric acid, methylamine, dimethylamine, ethamine, piperazine, aniline, sodium amide, lithium diisopropylamine, amination potassium, is not particularly limited.These nitrogen-containing compounds can use one, can also use two or more simultaneously.Ratio while using two or more nitrogen-containing compounds is not particularly limited.In these nitrogen-containing compounds, preferred material is inorganic metal amide compound, organic amine compound, and particularly preferred material is inorganic metal amide compound.
The metallic iron that the manufacture method process of the ferromagnetism nitrided iron particle powder of the present invention 2 method is 5～300nm by average grain long axis length and nitrogen-containing compound are 200 ℃ of operations of heat-treating below, cleaning afterwards.
When the heat treatment temperature of the mixture of metallic iron and nitrogen-containing compound exceedes 200 ℃, with Fe 4other mixes existence mutually N etc.Be preferably 100～200 ℃, more preferably 100～190 ℃.Processing time is not particularly limited, and is preferably 3～120 hours, more preferably 3～100 hours.
Cleaning is not particularly limited, and can use ethanol or the methyl alcohol etc. of dehydration.Cleaning solvent amount is not particularly limited, and uses 100ml above with respect to ferromagnetism nitrided iron particle powder 1g.Cleaning method is not particularly limited, and can apply the cleaning method of use Bu Shi suction funnel, pressure filter, glass filter, whizzer etc.Dry can suitably utilize natural drying, vacuumize, (vacuum) freeze-drying, evaporator etc.
The average major axis length of the ferromagnetism nitrided iron particle powder that the manufacture method of the method by the present invention 2 makes is 5～300nm.Shape is not particularly limited, can be needle-like, spindle shape, grain of rice shape, spherical, granular, hexahedron shape, octahedra shape any.At this, average major axis length represents the length from the long side of the shape of primary particle, refers to diameter when spherical.The average major axis length needing can suitably be selected according to its purposes.
The ferromagnetism nitrided iron particle powder of the present invention 2 method can be by coated with silica.Coated with silica thickness is, below 20nm, to be preferably below 17nm.
Below, the present invention 5 method is described.
First, the iron compound using in the present invention 5 method is described.
As iron compound, alpha-feooh, β-FeOOH, γ-FeOOH, α-Fe 2o 3, β-Fe 2o 3, Fe 3o 4, γ-Fe 2o 3, ferric oxalate, ferric acetate, ferric nitrate, ferric stearate, iron oleate etc. all can, be not particularly limited.In addition, can use one, also can use two or more simultaneously.Use the ratio of the each compound when two or more to be not particularly limited.Shape is not particularly limited, can be needle-like, spindle shape, grain of rice shape, spherical, granular, hexahedron shape, octahedra shape etc. any.
In the situation that using FeOOH, while carrying out processed as required, the temperature of processed is preferably 80～350 ℃.When they are during lower than 80 ℃, dewater hardly.In the time that it exceedes 350 ℃, in ensuing reduction is processed, be difficult to obtain at low temperatures iron granule powder.More preferably processed temperature is 85～300 ℃.
Reducing agent in the present invention 5 can by will be selected from least a kind of above compound in metal hydride, metal halide, metallic boron hydrides and iron compound mix and heat-treat and obtain.As the concrete example of these reducing agents, can enumerate: the metal hydrides such as dimethyl hydrogenation aluminium, diisobutyl aluminium hydride, calcium hydride, magnesium hydride, sodium hydride, hydrofining, lithium hydride, titantium hydride, zircoium hydride, the metal halide such as magnesium borohydride, sodium borohydride, or the metallic boron hydrides such as isopropyl halogenation magnesium, gallium halide, indium halide, tin halides, zinc halide, halogenation cadmium, copper halide, nickel halogenide, manganese halide, sodium aluminum hydride.These reducing agents can use one, also can use two or more simultaneously.Ratio while using two or more reducing agents is not particularly limited.
It is in good condition that reducing agent carries out as powder and iron compound and nitrogen-containing compound that dry type mixes, and preferably with mortar etc., iron compound, nitrogen-containing compound and reducing agent pulverized, mixed in advance.
In addition, particularly in reducing agent, contain the situation of water constituent and the absorption of moisture violent, be preferably dried in advance or the pre-heat treatment.
The blending ratio of iron compound and reducing agent is not particularly limited, and is 0.5～50 with respect to the weight ratio of iron compound, is preferably 0.8～30.
The nitrogen-containing compound that is used for the ferromagnetism nitrided iron particle powder that obtains the present invention 5 is solid or the liquid such as urea, ammoniacal liquor, ammonium chloride, nitric acid, methylamine, dimethylamine, ethamine, piperazine, aniline, sodium amide, lithium diisopropylamine, amination potassium, is not particularly limited.These nitrogen-containing compounds can use one, can also use two or more simultaneously.Ratio while using two or more nitrogen-containing compounds is not particularly limited.In these nitrogen-containing compounds, preferred material is inorganic metal amide compound, organic amine compound, and particularly preferred material is inorganic metal amide compound.
The blending ratio of iron compound and nitrogen-containing compound is not particularly limited, and is 0.5～50 with respect to the weight ratio of iron compound, is preferably 0.8～30.
The purity of reducing agent is not particularly limited.While considering the validity of reducing agent and cost, for example, be 50～99.9%, be preferably 60～99%.
The iron compound that is used for the ferromagnetism nitrided iron particle powder that obtains the present invention 5 can be by coated with silica.Coated with silica thickness is, below 20nm, to be preferably below 17nm.
Preferably in atmosphere or glove box etc. can regulate in the equipment of atmosphere, humidity, temperature and weigh iron compound, reducing agent and nitrogen-containing compound, afterwards, pulverize, mix with mortar etc.
The present invention 5 ferromagnetism nitrided iron particle powder is by obtaining through the operation of iron compound being carried out to reduction and nitrogenize in same operation and clean.
As the heat treatment method of iron compound, reducing agent and nitrogen-containing compound, standing type, mobile any all can, preferably in closed container, carry out.If under laboratory level, for example, can consider the method for the mixture of enclosing iron compound, reducing agent and nitrogen-containing compound in glass tube.In addition, pilot plant's scale if can be for enclosing the mixture of iron compound, reducing agent and nitrogen-containing compound on one side and it flowed, the method for heat-treating on one side in metal tube.
The heat treatment temperature of the mixture of iron compound, reducing agent and nitrogen-containing compound is 50～280 ℃.The reduction temperature that heat treatment temperature has separately according to the kind of reducing agent and addition, iron compound is determined, is preferably 80～275 ℃, more preferably 100 ℃～250 ℃.When excess Temperature, with Fe 4other mixes existence mutually N etc.In addition, the heat treated time is preferably 0.5 hour～and 7 days, more preferably 1 hour～3 days.
Continuous oven or RF coreless induction furnace etc. can be suitably selected in heat treatment.
Cleaning is not particularly limited, and can use ethanol or the methyl alcohol etc. of dehydration.Cleaning solvent amount is not particularly limited, and uses 100ml above with respect to ferromagnetism nitrided iron particle powder 1g.Cleaning method is not particularly limited, and can apply the cleaning method of use Bu Shi suction funnel, pressure filter, glass filter, whizzer etc.Dry can suitably utilize natural drying, vacuumize, (vacuum) freeze-drying, evaporator etc.
The average grain long axis length of the ferromagnetism nitrided iron particle powder obtaining by the present invention 5 is 5～150nm, and principal phase is ferromagnetism nitrided iron.In ferromagnetism nitrided iron particle powder in average grain long axis length lower than 5nm, the atom contacting with particle surface interface exists in a large number, therefore, even if obtain ferromagnetism nitrided iron particle powder, can not expect large magnetization.In the time that it exceedes 150nm, nitrogenize is difficult to carry out, metallic iron and Fe 4n etc. mix existence.Be preferably 5～140nm, more preferably 6～135nm.
The shape of the ferromagnetism nitrided iron particle powder obtaining by the present invention 5 is not particularly limited, can be needle-like, spindle shape, grain of rice shape, spherical any.At this, average major axis length represents the length from the long side of the shape of primary particle, refers to diameter when spherical.The average major axis length needing can suitably be selected according to its purposes.
Below, the ferromagnetism nitrided iron particle powder making by the present invention 1,2 and 5 manufacture method is described.
The ferromagnetism nitrided iron particle powder making by the present invention 1,2 and 5 method, preferably according to Mo&4&ssbauer spectrum data Fe 16n 2compound Phase is more than 80%.In Mo&4&ssbauer spectrum, generating Fe 16n 2time, confirm that internal magnetic field is the peak in iron site more than 330kOe, special feature is near the peak that occurs that 395kOe is.Conventionally, when other are mutually more, show consumingly the characteristic as soft magnet, thereby be not suitable as ferromagnetism rigid magnet material.But, in the present invention, can give full play to characteristic as ferromagnetism rigid magnet material.
The ferromagnetism nitrided iron particle powder making by the present invention 1,2 and 5 method, particle cores is Fe 16n 2, there is FeO in particle shell, preferably from the core of particle to shell by Fe 16n 2the simple structure of/FeO forms.Preferably Fe 16n 2with FeO local structured combination, in crystallography continuously.In the oxide-film of this shell, can contain Fe 3o 4or Fe 2o 3, α-Fe.At Fe 16n 2when particle is low-purity, comprise sometimes these impurity, but be only FeO by high-purityization.The thickness of FeO is, below 5nm, to be preferably below 4nm.Along with Fe 16n 2high-purity, this FeO thickness attenuation.FeO thickness is not particularly limited, but contained Fe in thinner particle 16n 2percentage by volume is higher, thereby preferably.The lower limit of FeO thickness is not particularly limited, and is 0.5nm left and right.
The percentage by volume of the FeO on the ferromagnetism nitrided iron particle powder surface making by the present invention 1,2 and 5 method, with the whole stereometers of FeO volume/particle, is preferably below 25%.By by Fe 16n 2high-purity, the percentage by volume of FeO reduces.More preferably the percentage by volume of FeO is below 23%, more preferably 3～20%.
The preferred coercive force H of ferromagnetism nitrided iron particle powder making by the present invention 1,2 and 5 method csaturation magnetization σ for 1.5kOe is above, when 5K smore than 150emu/g.Wherein, in the present invention, being defined as of " ferromagnetism " at least meets above-mentioned magnetic characteristic.Saturation magnetisation value σ swith coercive force H cduring lower than above-mentioned scope, it is hard to tell that as retentive material magnetic characteristic is abundant.More preferably coercive force H cfor 1.6kOe is above, saturation magnetisation value σ smore than 180emu/g.
The ferromagnetism nitrided iron particle powder making by the present invention 1,2 and 5 method, the nitriding rate of being obtained by lattice constant is preferably 8～13mol%.By Fe 16n 2the 11.1mol% that obtains of chemical constitution formula the most applicable.More preferably nitriding rate is 8.5～12.5mol%, more preferably 9.0～12mol%.
The BET specific area of the ferromagnetism nitrided iron particle powder making by the present invention 1,2 and 5 method is preferably 5.0～40m 2/ g.BET specific area is less than 5m 2when/g, nitriding rate reduces, result Fe 16n 2production rate decline, can not obtain expection coercive force and saturation magnetization.If be greater than 40m 2/ g, just can not obtain the saturation magnetisation value of expecting.More preferably BET specific area is 5.5～38m 2/ g, more preferably 6.0～35m 2/ g.
Below, the anisotropic magnet that comprises the ferromagnetism nitrided iron particle powder making by the present invention 2 method and the present invention 5 method is described.
The magnetic characteristic of anisotropic magnet of the present invention can be adjusted according to object purposes, to obtain the magnetic characteristic (coercive force, residual magnetic flux density, maximum magnetic energy product) of expection.
The method of carrying out magnetic aligning is not particularly limited.For example, the temperature more than vitrification point, in the copolymerization of EVA(ethylene-vinyl acetate) in resin, will be according to Mo&4&ssbauer spectrum with Fe 16n 2compound Phase is mixing and molding together with ferromagnetism nitrided iron particle powder and the dispersant etc. that more than 80% form, and applies desirable external magnetic field near the temperature of that exceedes vitrification point, can promote magnetic aligning.Or, utilize coating oscillator etc. by the resins such as polyurethane, organic solvent and this ferromagnetism nitrided iron particle powder powerful mixing, pulverize and obtain ink, utilization scrape the skill in using a kitchen knife in cookery or Roll-to-Roll method by this ink coating and printing obtaining on resin molding, in magnetic field, pass through rapidly, can make its magnetic aligning.In addition, also can use RIP(Resin Isostatic Pressing: the static pressure such as resin), carry out high density more and bring into play to greatest extent the magnetic aligning of crystallization magnetic anisotropy.Can be in advance ferromagnetism nitrided iron particle powder be carried out to the insulating wrapped of silicon dioxide or aluminium oxide, zirconia, tin oxide, antimony oxide etc.The method of insulating wrapped is not particularly limited, can be for making it the method for absorption or utilize CVD etc. to carry out evaporation by controlling particle surface current potential in solution.
Below, the resin composition for bonded magnet that contains the ferromagnetism nitrided iron particle powder making by the present invention 2 method and the present invention 5 method is described.
Resin composition for bonded magnet of the present invention is dispersed in ferromagnetism nitrided iron particle powder of the present invention in adhesive resin and forms, this ferromagnetism nitrided iron particle powder that contains 85～99 % by weight, remainder is made up of adhesive resin and other additive.
Can be in advance ferromagnetism nitrided iron particle powder be carried out to the insulating wrapped of silicon dioxide or aluminium oxide, zirconia, tin oxide, antimony oxide etc.The method of insulating wrapped is not particularly limited, can be for making it the method for absorption or utilize CVD etc. to carry out evaporation by controlling particle surface current potential in solution.
As above-mentioned adhesive resin, can carry out various selections according to forming method, the in the situation that of injection moulding, extrusion molding and calendering formation, can use thermoplastic resin, the in the situation that of compression forming, can use thermosetting resin.As above-mentioned thermoplastic resin, for example, can use the resin of nylon (PA) class, polypropylene (PP) class, ethylene-vinyl acetate (EVA) class, polyphenylene sulfide (PPS) class, liquid crystalline resin (LCP) class, elastomer class, rubber-like etc.As above-mentioned thermosetting resin, for example, can use the resin of epoxies, phenolic etc.
In addition, manufacturing when resin composition for bonded magnet, for easy moulding or give full play to magnetic characteristic, as required, except using adhesive resin, can also use the well-known additives such as plasticizer, lubricant, coupling agent.In addition, can also mixed ferrite ferromagnetic powder etc. the ferromagnetic powder of other kind.
These additives can suitably be selected according to object, as plasticizer, can use the commercially available product corresponding with the resin-phase using separately, and its total amount is 0.01～5.0 % by weight left and right with respect to the adhesive resin using.
As above-mentioned lubricant, can use stearic acid and derivative thereof, inorganic lubricant, oils etc., with respect to whole binding magnets, its consumption can be 0.01～1.0 % by weight left and right.
As above-mentioned coupling agent, can use the commercially available product corresponding with the resin using and filler, with respect to the adhesive resin using, its consumption can be 0.01～3.0 % by weight left and right.
Resin composition for bonded magnet of the present invention, by ferromagnetism nitrided iron particle powder is mixed with adhesive resin, mixing, obtains resin composition for bonded magnet.
Above-mentioned mixing can utilize mixer of Henschel mixer, V word mixer, nauta mixer etc. etc. to carry out, and mixing single shaft mixing roll, twin shaft mixing roll, mortar type mixing roll, the extruder and mixing roll etc. of can utilizing carry out.
Below, binding magnet of the present invention is described.
The magnetic characteristic of binding magnet can be adjusted according to object purposes, to obtain the magnetic characteristic (coercive force, residual magnetic flux density, maximum magnetic energy product) of expection.
Binding magnet of the present invention, by using above-mentioned resin composition for bonded magnet, carry out processing and forming with well-known forming methods such as injection moulding, extrusion molding, compression forming or calendering formations, afterwards according to usual method, magnetize or pulsed field magnetization by electromagnet, obtain binding magnet.
Then, sintered magnet of the present invention is described.
Sintered magnet of the present invention, carries out compression forming and heat treatment can obtain to ferromagnetism nitrided iron particle powder.The condition of magnetic field and compression forming is not particularly limited, and can adjust the required value of the powder magnet that obtains making.For example, can enumerate magnetic field is that 1～15T, compression forming pressure are 1.5～15ton/cm 2.Forming machine is not particularly limited, and can use CIP or RIP.The shape of formed body and size can be selected according to purposes.
Can be in advance ferromagnetism nitrided iron particle powder be carried out to the insulating wrapped of silicon dioxide or aluminium oxide, zirconia, tin oxide, antimony oxide etc.The method of insulating wrapped is not particularly limited, can be for making it the method for absorption or utilize CVD etc. to carry out evaporation by controlling particle surface current potential in solution.
As lubricant, can use stearic acid and derivative thereof, inorganic lubricant, oils etc., with respect to whole binding magnets, its consumption is 0.01～1.0 % by weight left and right.
As adhesive, can be with respect to whole binding magnets, use the thermoplastic resin of the TPO such as polyethylene, polypropylene, polyvinyl alcohol, polyethylene glycol oxide, PPS, liquid crystal polymer, PEEK, polyimides, Polyetherimide, polyacetals, polyether sulfone, polysulfones, Merlon, PETG, polybutylene terephthalate (PBT), polydiphenyl ether, polyphthalamide, polyamide etc. of 0.01～5.0 % by weight left and right or their mixture.
Continuous oven or RF coreless induction furnace etc. can be suitably selected in heat treatment.Heat-treat condition is not particularly limited.
Then, powder magnet of the present invention is described.
Powder magnet of the present invention, can obtain the ferromagnetism nitrided iron particle powder compression forming in magnetic field obtaining.The condition of magnetic field and compression forming is not particularly limited, and can adjust the required value of the powder magnet that obtains making.For example, can enumerate magnetic field is that 1.0～15T, compression forming pressure are 1.5～15ton/cm 2.Forming machine is not particularly limited, and can use CIP or RIP.The shape of formed body and size can be selected according to purposes.
Can be in advance ferromagnetism nitrided iron particle powder be carried out to the insulating wrapped of silicon dioxide or aluminium oxide, zirconia, tin oxide, antimony oxide etc.The method of insulating wrapped is not particularly limited, can be for making it the method for absorption or utilize CVD etc. to carry out evaporation by controlling particle surface current potential in solution.
As lubricant, can use stearic acid and derivative thereof, inorganic lubricant, oils etc., with respect to whole binding magnets, its consumption is 0.01～1.0 % by weight left and right.
As adhesive, can be with respect to whole binding magnets, use the thermoplastic resin of the TPO such as polyethylene, polypropylene, polyvinyl alcohol, polyethylene glycol oxide, PPS, liquid crystal polymer, PEEK, polyimides, Polyetherimide, polyacetals, polyether sulfone, polysulfones, Merlon, PETG, polybutylene terephthalate (PBT), polydiphenyl ether, polyphthalamide, polyamide etc. of 0.01～5.0 % by weight left and right or their mixture.
Continuous oven or RF coreless induction furnace etc. can be suitably selected in heat treatment.Heat-treat condition is not particularly limited.
Embodiment
, utilize embodiment to describe in further detail the present invention below, but following embodiment is only illustration, the present invention is not limited to following embodiment.Following embodiment 1-1～1-3 and comparative example 1-1 be about the present invention 1～4 manufacture method and use the example of the magnet of the ferromagnetism nitrided iron particle powder that obtains thus, and embodiment 2-1～2-5 and comparative example 2-1 are about the present invention 1 and 5～8 manufacture method and use the example of the magnet of the ferromagnetism nitrided iron particle powder obtaining thus.The evaluation method using in following embodiment and comparative example is described.
The specific area value of sample is measured by the B.E.T. method of utilizing nitrogen.
The size of iron compound, metallic iron, ferromagnetism nitrided iron particle powder is used transmission electron microscope (Jeol Ltd., JEM-1200EX II) to measure.Choose randomly 120 particles and measure particle size, obtain mean value.
Initiation material and the formation of the ferromagnetism nitrided iron particle powder obtaining utilize powder x-ray diffraction device (XRD, the RUKER of Co., Ltd. B produce, D8ADVANCE) to identify mutually, use the electron ray diffraction (ED) of transmission electron microscope (Jeol Ltd., JEM-2000EX), electron ray light splitting type superelevation resolution electron microscope (HREM, Hitachi High-Technologies Corporation, HF-2000) and determine.With regard to XRD determining, in glove box, the sample that ferromagnetism nitrided iron particle powder is blended in silicone grease is measured.
The magnetic characteristic of the ferromagnetism nitrided iron particle powder obtaining, is used physical characteristic to measure system (PPMS+VSM, Quantum Design Japan, Inc.), measures in the magnetic field of 0～9T with room temperature (300K).Also carry out in addition the temperature dependency evaluation of the magnetic susceptibility of 5K～300K.Embodiment 1-1:
The preparation > of < metallic iron
In the kerosene solvent 50ml that is added with oleyl amine (10 times of metallic iron weight ratios) that stir with stirrer, 180 ℃, make iron pentacarbonyl gas flow into 10 minutes and keep 1h with 30ml/min, obtain thus the spherical iron granule of average grain long axis length (=diameter) for 9.7nm.It is carried out in glove box, after centrifugation, carry out washed with methanol, obtain the slurry of metallic iron.
< coated with silica >
Then, at cyclohexane (reagent) 48.75g, TEOS(tetraethoxysilane, the reagent of dehydration) add the slurry, the Igepal CO-520(reagent that are equivalent to this metallic iron solid constituent 15mg in the solvent of 0.4g) 3.65g, be uniformly mixed fully.Then, add the 28wt% ammoniacal liquor (reagent) of 0.525ml, under room temperature (25 ℃), carry out the stirring of 28h blender.Thereafter, centrifugation in glove box, carries out washed with methanol afterwards.The sample obtaining is confirmed as metallic iron by XRD, and coated with silica thickness is 13nm.
The preparation > of < ferromagnetism nitrided iron particle powder
Iron granule 0.8g, the ammonium chloride 2.5g and the sodium amide 2.5g that have carried out above-mentioned coated with silica are mixed lightly with agate mortar in glove box, and vacuum is enclosed in glass tube.Then, put it in electric furnace, carry out the heat treatment of 48h, quenching taking-up with 130 ℃.Again put into glove box, from glass tube, take out sample, fully carry out washed with methanol, remove impurity with the processing of whizzer.
The analysis of the sample that < obtains, evaluation >
Confirm that by XRD the sample obtaining is ferromagnetism nitrided iron Fe 16n 2single-phase.The average grain long axis length (=diameter) of ferromagnetism nitrided iron particle is 9.7nm, and coated with silica thickness is 13nm.In addition, the saturation magnetization when 5K of ferromagnetism nitrided iron part is 214emu/g in the 14.5kOe of magnetic field.
Embodiment 1-2:
In the removable flask of four-hole, on one side with 500ml/min circulation argon gas, add ethylene glycol 0.25L, granular NaOH 7.2g, oleyl amine 0.67g, ferric acetyl acetonade 6.39g, acetylacetone,2,4-pentanedione platinum 0.15g on one side, stir while be warming up to 125 ℃.Keep, after 1h, being warming up to 185 ℃, keep 2.5h.,, be cooled to room temperature thereafter.In separatory funnel, prepare dehydration hexane 250ml, move into wherein reacted sample.Send ultrasonic wave fully vibration on one side on one side from outside, thus, the nano particle of generation is transferred to hexane solvent from ethylene glycol.The hexane that has moved into nano particle is moved in the beaker of 50ml, in draft chamber, carry out natural drying.The powder of nanometric particles obtaining is γ-Fe 2o 3, be that average grain long axis length is the roughly spherical particle of 16nm.
Then, by this γ-Fe 2o 3after 5g and calcium hydride (reagent) 85g mixes lightly, put into the stainless steel container made that can vacuumize, be formed as vacuum.Used electric furnace with 200 ℃ of heat treatment 25h, moved in glove box.Fully clean impurity and be dried with methyl alcohol, obtaining metallic iron powder.
This metallic iron powder 0.8g, ammonium chloride 3.5g, sodium amide 1.0g, urea 0.5g are mixed lightly with agate mortar in glove box, and vacuum is enclosed in glass tube.Then, put it in electric furnace, carry out the heat treatment of 30h, quenching taking-up with 135 ℃.Again put into glove box, from glass tube, take out sample, fully carry out washed with methanol, remove impurity with the processing of whizzer.
Confirm that by XRD the sample obtaining is ferromagnetism nitrided iron Fe 16n 2single-phase.The average grain long axis length (=diameter) of ferromagnetism nitrided iron particle is 13nm.In addition, the saturation magnetization when 5K of ferromagnetism nitrided iron particle powder is 206emu/g in the 14.5kOe of magnetic field.
Embodiment 1-3:
In beaker, take iron chloride six water salt 27.05g, make 500ml with pure water.Add therein urea 2.12g, at stirring at room temperature 30min.Then, this solution is moved in the pressure vessel of enclosed system, stir with 200rpm with agitator on one side, on one side with 85 ℃ of reaction 3.5h.Used Bu Shi suction funnel to carry out isolated by filtration, use with respect to the pure water of 1g sample 30ml pure water and fully clean.The sample obtaining is the needle-like akaganeite of average grain long axis length 130nm.40 ℃ of dry 1 nights, in hydrogen stream, with 282 ℃ of reductase 12 h, in glove box, take out.The sample obtaining is that α-Fe of average major axis length 123nm is single-phase.
This metallic iron powder 2g, ammonium chloride 5.0g and sodium amide 1.0g are mixed lightly in glove box, and vacuum is enclosed in glass tube.Then, put it in electric furnace, carry out the heat treatment of 18h, quenching taking-up with 145 ℃.Again put into glove box, from glass tube, take out sample, fully carry out washed with methanol, remove impurity with the processing of whizzer.
Confirm that by XRD the sample obtaining is ferromagnetism nitrided iron Fe 16n 2single-phase.The average grain long axis length of ferromagnetism nitrided iron particle is 123nm.In addition, the saturation magnetization when 5K of ferromagnetism nitrided iron particle powder is 218emu/g in the 14.5kOe of magnetic field.
Comparative example 1-1:
Frerrous chloride four water salt 180g are dissolved in the pure water of 2L, are adjusted to 22 ℃.With 10L/min ventilating air, after 10 minutes, with the aqueous solution that adds lentamente the 209ml that is dissolved with 11.16g NaOH for 20 minutes, pH is 7.0.After 1 hour, pH is reached to 6.7 reaction solution 100ml and move in 300ml glass beaker, at room temperature make stirrer rotate with 300rpm, reaction 24h.Used Bu Shi suction funnel isolated by filtration, use with respect to the pure water of 5g sample 200ml pure water and fully clean.
The sample obtaining is average grain long axis length 2700nm, aspect ratio 45.0, specific area 83.2m 2the needle-like lepidocrocite particle of/g.With 120 ℃ of dry 1 nights, then, carry out the heat treatment of 1h with 350 ℃.With the mixing and kneading machine pulverizing 1h that uses agate mortar.Further only extract the agglutinating particle below 180 μ m with vibrating screen.
Then, in hydrogen stream, carry out the reduction processing of 3h with 260 ℃.And the mist that the mixing mol ratio that makes nitrogen and hydrogen is on one side 3:1 is with total amount 10L/min circulation, carries out 9h nitrogen treatment on one side with 148 ℃.Thereafter, circulation argon gas, is cooled to room temperature, stops argon gas feed, carries out nitrogen displacement with 3h.Then, in the glove box directly linking, take out sample.
Confirm that by XRD the particle powder obtaining is only α-Fe metal, do not generate ferromagnetism nitrided iron.
Embodiment 2-1:
The generation > of < iron granule
In three mouthfuls of removable flasks of water white glass system (100mL) that air-cooled type return duct and thermometer are installed, add dioctyl ether (Aldrich reagent processed) 25mL and oleyl amine (Aldrich reagent processed) 8mmol.Dioctyl ether and oleyl amine use in advance the material after room temperature～50 ℃ use rotary pump carries out vacuumizing for 1 hour.
In addition, iron pentacarbonyl (Kanto Kagaku K. K.'s reagent processed) 2mmol is dissolved in a part (dioctyl ether+oleyl amine) 2mL of the solution in flask to raw materials solution.Utilize bell-type heater that the solution in the flask of argon gas bubbling is heated to 200 ℃, this material solution is injected without a break with syringe.After injection, generate immediately the spherical iron granule of 5nm.Material solution further heats and reflux 30 minutes (289 ℃ of the temperature of reactant liquor) after injecting, and removes afterwards thermal source, lets cool to room temperature, makes the mist bubbling 1h of oxygen/argon=0.5:99.5vol%, makes the particle surface 0.8nm oxidation of metallic iron.
Generate in liquid (10mL) and add dewatered ethanol (Wako Pure Chemical Industries, Ltd.'s reagent processed) 30mL at the sample particle obtaining, generate the insoluble matter of black, afterwards, carry out centrifugation, further remove supernatant by decant.
Wherein, above operation is all carried out in the glove box of the argon atmosphere below 10ppm at oxygen and moisture.
< coated with silica >
Then, with respect to the sample powder 90mg obtaining, weigh respectively Igepal CO-520(Aldrich company and produce) 3.65g, cyclohexane (Wako Pure Chemical Industries, Ltd.'s reagent processed) 48.75g, 28% ammoniacal liquor (Wako Pure Chemical Industries, Ltd.'s reagent processed) 0.38ml, tetraethoxysilane (Nacalai tesque Co., Ltd. reagent processed) 0.4g.First, in the removable flask of four-hole, add cyclohexane, then, drop into sample powder, the Igepal CO-520 of 5nm, start the stirring of 160rpm with fluororesin agitator processed.Temperature keeps room temperature, continuous stirring 0.5h.Then, drop into wherein tetraethoxysilane, afterwards, drop into 28% ammoniacal liquor.Under the state stirring, keep 18h.
In the sample obtaining, average grain long axis length (=diameter) is the iron compounds particle surface of the 5nm layer 6nm that be roughly coated with silicon oxide equably.
The preparation > of < ferromagnetism nitrided iron particle powder
Take out coated with silica iron compounds particle obtained above with whizzer, to be taken out in air with the powder after evaporator dry, this powder 0.8g and ammonium chloride (Wako Pure Chemical Industries, Ltd.'s reagent processed) 2.5g, sodium amide (Nacalai tesque Co., Ltd. reagent processed) 2.5g are mixed lightly with agate mortar in glove box, and vacuum is enclosed in glass tube.Then, put it in electric furnace, carry out the heat treatment of 48h, quenching taking-up with 130 ℃.Again put into glove box, from glass tube, take out sample, fully carry out washed with methanol, remove impurity with the processing of whizzer.
The analysis of the sample that < obtains, evaluation >
Confirm that by XRD the sample obtaining is ferromagnetism nitrided iron Fe 16n 2single-phase.The average grain long axis length (=diameter) of ferromagnetism nitrided iron particle is 4nm, and coated with silica thickness is 6nm.In addition, the saturation magnetization when 5K of ferromagnetism nitrided iron part is 216emu/g in the 14.5kOe of magnetic field.
Embodiment 2-2:
The preparation > of < metallic iron
In the kerosene solvent 50ml that is added with oleyl amine (10 times of metallic iron weight ratios) that stir with stirrer, 180 ℃, make iron pentacarbonyl gas flow into 10 minutes with 30ml/min, and keep 1h, obtain thus the spherical iron granule that average grain long axis length (=diameter) is 9.7nm.It after centrifugation, is carried out to washed with methanol in glove box, obtain the slurry of metallic iron.
< coated with silica >
Then, in the solvent of cyclohexane (Wako Pure Chemical Industries, Ltd.'s reagent processed) 48.75g, tetraethoxysilane (Wako Pure Chemical Industries, Ltd.'s reagent processed) 0.4g that dewater, add the slurry, the Igepal CO-520(Aldrich reagent processed that are equivalent to this metallic iron solid constituent 15mg) 3.65g, be uniformly mixed fully.Then, add the 28wt% ammoniacal liquor (Wako Pure Chemical Industries, Ltd.'s reagent processed) of 0.525ml, at room temperature carry out the stirring of 28h blender.,, in air, after centrifugation, carry out washed with methanol thereafter.The sample obtaining is γ-Fe of average grain long axis length (=diameter) 9.7nm 2o 3, coated with silica thickness is 13nm.
The preparation > of < ferromagnetism nitrided iron particle powder
Above-mentioned sample powder 0.8g and ammonium chloride (Wako Pure Chemical Industries, Ltd.'s reagent processed) 2.5g, sodium amide (Nacalai tesque reagent processed) 2.5g are mixed lightly with agate mortar in glove box, and vacuum is enclosed in glass tube.Then, put it in electric furnace, carry out the heat treatment of 48h, quenching taking-up with 130 ℃.Again put into glove box, from glass tube, take out sample, fully carry out washed with methanol, remove impurity with the processing of whizzer.
The analysis of the sample that < obtains, evaluation >
Confirm that by XRD the sample obtaining is ferromagnetism nitrided iron Fe 16n 2single-phase.The average grain long axis length (=diameter) of ferromagnetism nitrided iron particle is 8.4nm, and coated with silica thickness is 13nm.In addition, the saturation magnetization when 5K of ferromagnetism nitrided iron part is 221emu/g in the 14.5kOe of magnetic field.
Embodiment 2-3:
The preparation > of < metallic iron
In the removable flask of four-hole, one side is with 500ml/min circulation argon gas, add ethylene glycol (Wako Pure Chemical Industries, Ltd.'s reagent processed) 0.25L, granular NaOH (Nacalai tesque Co., Ltd. reagent processed) 7.2g, oleyl amine (Wako Pure Chemical Industries, Ltd.'s reagent processed) 0.67g, ferric acetyl acetonade (Aldrich reagent processed) 6.39g, acetylacetone,2,4-pentanedione platinum (Wako Pure Chemical Industries, Ltd.'s reagent processed) 0.15g on one side, stir on one side, be warming up to 125 ℃ on one side.After keeping 1h, be warming up to 185 ℃, keep 2.5h.,, be cooled to room temperature thereafter.In separatory funnel, prepare dehydration hexane (Wako Pure Chemical Industries, Ltd.'s reagent processed) 250ml, move into wherein reacted sample.Send ultrasonic wave fully vibration on one side on one side from outside, thus, the nano particle of generation is transferred to hexane solvent from ethylene glycol.The hexane that has moved into nano particle is moved in the beaker of 50ml, in draft chamber, carry out natural drying.The powder of nanometric particles obtaining is γ-Fe 2o 3, be the roughly spherical particle of average grain long axis length (=diameter) 16nm.
The preparation > of < ferromagnetism nitrided iron particle powder
Then, by this γ-Fe 2o 30.5g and calcium hydride (Wako Pure Chemical Industries, Ltd.'s reagent processed) 8.5g mixes lightly, ammonium chloride (Wako Pure Chemical Industries, Ltd.'s reagent processed) 3g, sodium amide (Nacalai tesque Co., Ltd. reagent processed) 0.3g, urea (Wako Pure Chemical Industries, Ltd.'s reagent processed) 0.1g are mixed lightly with agate mortar in glove box, vacuum is enclosed in glass tube again.Then, put it in electric furnace, carry out the heat treatment of 40h, quenching taking-up with 128 ℃.Again put into glove box, from glass tube, take out sample, fully carry out washed with methanol, remove impurity with the processing of whizzer.
The analysis of the sample that < obtains, evaluation >
Confirm that by XRD the sample obtaining is ferromagnetism nitrided iron Fe 16n 2single-phase.The average grain long axis length (=diameter) of ferromagnetism nitrided iron particle is 13nm.In addition, the saturation magnetization when 5K of ferromagnetism nitrided iron particle powder is 206emu/g in the 14.5kOe of magnetic field.
Embodiment 2-4:
In beaker, take iron chloride six water salt (Wako Pure Chemical Industries, Ltd.'s reagent processed) 27.05g, make 500ml with pure water.Add wherein urea 2.12g, at room temperature stir 30min.Then, this solution is moved in the pressure vessel of enclosed system, stir with 200rpm with agitator on one side, on one side with 85 ℃ of reaction 3.5h.Used Bu Shi suction funnel to carry out isolated by filtration, use with respect to the pure water of 1g sample 30ml pure water and clean fully.The sample obtaining is the needle-like akaganeite of average grain long axis length 130nm.
This iron compound powder 2g and ammonium chloride (Wako Pure Chemical Industries, Ltd.'s reagent processed) 5.0g, sodium amide (Nacalai tesque Co., Ltd. reagent processed) 1.5g are mixed lightly in glove box, and vacuum is enclosed in glass tube.Then, put it in electric furnace, carry out the heat treatment of 18h, quenching taking-up with 145 ℃.Again put into glove box, from glass tube, take out sample, fully carry out washed with methanol, remove impurity with the processing of whizzer.
Confirm that by XRD the sample obtaining is ferromagnetism nitrided iron Fe 16n 2single-phase.The average grain long axis length of ferromagnetism nitrided iron particle is 118nm.In addition, the saturation magnetization when 5K of ferromagnetism nitrided iron particle powder is 218emu/g in the 14.5kOe of magnetic field.
Embodiment 2-5:
Ferric acetate (II) (with the pure medicine of light reagent processed) 25mg, sodium hydride (with the pure medicine of light reagent processed) 25mg, ammonium chloride (with the pure medicine of light reagent processed) 75mg, sodium amide (Nacalai tesque Co., Ltd. reagent processed) 75mg are mixed fully in glove box, and vacuum is enclosed in glass tube.Then, put it in electric furnace, carry out the heat treatment of 20h, quenching taking-up with 125 ℃.Again put into glove box, from glass tube, take out sample, fully carry out washed with methanol, remove impurity with the processing of whizzer.
Confirm that by XRD the sample obtaining is ferromagnetism nitrided iron Fe 16n 2principal phase, confirms micro-α-Fe.The average grain long axis length of ferromagnetism nitrided iron particle is 12nm.In addition, the saturation magnetization when 5K of ferromagnetism nitrided iron particle powder is 196emu/g in the 14.5kOe of magnetic field.
Comparative example 2-1:
Frerrous chloride four water salt 180g are dissolved in the pure water of 2L, are adjusted to 22 ℃.With 10L/min ventilating air, after 10 minutes, with the aqueous solution that adds lentamente the 209ml that is dissolved with 11.16g NaOH for 20 minutes, pH is 7.0.After 1 hour, the 100ml that pH is reached to 6.7 reaction solution moves in 300ml glass beaker, at room temperature makes stirrer rotate with 300rpm, reaction 24h.Used Bu Shi suction funnel isolated by filtration, use with respect to the pure water of 5g sample 200ml pure water and clean fully.
The sample obtaining is average grain long axis length 2700nm, aspect ratio 45.0, specific area 83.2m 2the needle-like lepidocrocite particle of/g.Make its dry 1 night with 120 ℃, then, carry out the heat treatment of 1h with 350 ℃.With the mixing and kneading machine pulverizing 1h that uses agate mortar.Only extract the agglutinating particle below 180 μ m with vibrating screen again.
Then, in hydrogen stream, carrying out 3h reduction with 260 ℃ processes.And the mist that the mixing ratio that makes ammonia, nitrogen and hydrogen is on one side 9.5:0.45:0.05 is with total amount 10L/min circulation, carries out 9h nitrogen treatment on one side with 148 ℃.Afterwards, circulation argon gas, is cooled to room temperature, stops argon gas feed, carries out nitrogen displacement with 3h.Then, in the glove box directly linking, take out sample.
Confirm that by XRD the particle powder obtaining is Fe 16n 2.The average grain long axis length of ferromagnetism nitrided iron particle is 2630nm.In addition, the saturation magnetization when 5K of ferromagnetism nitrided iron particle powder is 218emu/g in the 14.5kOe of magnetic field.
In comparative example 2-1, the total ascent time (comprising heating-up time, cooling time) of reduction operation and nitrogenize operation is 29.5 hours, needs long-time.In addition, use ammonia, the control difficulty of flow.
Utilizability in industry
The manufacture method of ferromagnetism nitrided iron particle powder of the present invention, can easily obtain the ferromagnetism nitrided iron particle powder of ferromagnetism nitrided iron particle powder, particularly particulate, therefore, is suitable as the manufacture method of ferromagnetism nitrided iron particle powder.

Claims (11)

1. a manufacture method for ferromagnetism nitrided iron particle powder, is characterized in that:
By metallic iron or iron compound and nitrogen-containing compound mixing, then heat-treat.
2. the manufacture method of ferromagnetism nitrided iron particle powder as claimed in claim 1, is characterized in that:
Metallic iron and nitrogen-containing compound are mixed, and the average grain long axis length of metallic iron is 5～300nm.
3. the manufacture method of ferromagnetism nitrided iron particle powder as claimed in claim 2, is characterized in that:
As metallic iron, use will be selected from least a kind of above compound and iron compound in metal hydride, metal halide, metallic boron hydrides mix, then heat-treat and the metallic iron that obtains.
4. the manufacture method of ferromagnetism nitrided iron particle powder as claimed in claim 2 or claim 3, is characterized in that:
As metallic iron, use the metallic iron that carries out coated with silica with the thickness below 20nm.
5. the manufacture method of ferromagnetism nitrided iron particle powder as claimed in claim 1, is characterized in that:
Iron compound, nitrogen-containing compound and reducing agent are mixed, then heat-treat.
6. the manufacture method of ferromagnetism nitrided iron particle powder as claimed in claim 5, is characterized in that:
In same operation, carry out reduction operation and the nitrogenize operation of iron compound.
7. the manufacture method of the ferromagnetism nitrided iron particle powder as described in claim 5 or 6, is characterized in that:
As the reducing agent in reduction operation, use at least a kind of above compound being selected from metal hydride, metal halide, metallic boron hydrides, and, as the nitrogenous source of nitrogenize operation, use nitrogen-containing compound.
8. the manufacture method of the ferromagnetism nitrided iron particle powder as described in any one in claim 5～7, is characterized in that:
As iron compound, use the iron compound of coated with silica.
9. a manufacture method for anisotropic magnet, this anisotropic magnet comprises ferromagnetism nitrided iron particle powder, described manufacture method is characterised in that:
Use the ferromagnetism nitrided iron particle powder making by the manufacture method of the ferromagnetism nitrided iron particle powder described in any one in claim 1～8.
10. a manufacture method for binding magnet, this binding magnet contains ferromagnetism nitrided iron particle powder, and this manufacture method is characterised in that:
Right to use requires the ferromagnetism nitrided iron particle powder described in any one in 1～8.
The manufacture method of 11. 1 kinds of powder magnets, this powder magnet contains ferromagnetism nitrided iron particle powder, and this manufacture method is characterised in that:
Use the ferromagnetism nitrided iron particle powder making by the manufacture method of the ferromagnetism nitrided iron particle powder described in any one in claim 1～8.
CN201280045918.7A 2011-09-22 2012-09-20 Method for manufacturing ferromagnetic iron nitride powder, anisotropic magnet, bond magnet, and compressed-powder magnet Pending CN103814417A (en)

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